Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

Andrew J. Smith, Allan Young, Simon Rohrbach, Erin F. O'Connor, Mark Allison, Hong-Shuang Wang, Darren L. Poole, Tell Tuttle, John A. Murphy

Research output: Contribution to journalArticle

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Abstract

Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.
LanguageEnglish
Pages13747–13751
Number of pages5
JournalAngewandte Chemie International Edition
Volume56
Issue number44
Early online date11 Sep 2017
DOIs
Publication statusPublished - 2 Oct 2017

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Addition reactions
Ethers
Complex networks
Sulfides
Hydrides
Potassium
Electrons
potassium tert-butoxide
triethylsilane

Keywords

  • electron-transfer reactions
  • hydride-transfer pathways
  • single-electron transfer
  • hydride delivery reactions

Cite this

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title = "Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)",
abstract = "Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.",
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Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH). / Smith, Andrew J.; Young, Allan; Rohrbach, Simon; O'Connor, Erin F.; Allison, Mark; Wang, Hong-Shuang; Poole, Darren L.; Tuttle, Tell; Murphy, John A.

In: Angewandte Chemie International Edition, Vol. 56, No. 44, 02.10.2017, p. 13747–13751.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

AU - Smith, Andrew J.

AU - Young, Allan

AU - Rohrbach, Simon

AU - O'Connor, Erin F.

AU - Allison, Mark

AU - Wang, Hong-Shuang

AU - Poole, Darren L.

AU - Tuttle, Tell

AU - Murphy, John A.

PY - 2017/10/2

Y1 - 2017/10/2

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AB - Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.

KW - electron-transfer reactions

KW - hydride-transfer pathways

KW - single-electron transfer

KW - hydride delivery reactions

U2 - 10.1002/anie.201707914

DO - 10.1002/anie.201707914

M3 - Article

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EP - 13751

JO - Angewandte Chemie International Edition

T2 - Angewandte Chemie International Edition

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